Heat resistant dyes for polyester film products

ABSTRACT

Certain azabenzanthrone and diazabenzanthrone dyes have been found A. TO BE PECULIARLY RESISTANT TO SPONTANEOUS HIGH TEMPERATURE DEGRADATION, AND B. TO BE PARTICULARLY USEFUL AS COLORANTS FOR PHOTOGRAPHIC FILM PRODUCTS MADE BY EXTRUDING A DYED POLYESTER FILM BASE. In combination with a green dye such as 1,4-dihydroxy-5,8-di-ptoluidino anthraquinone or 1,4-di-p-butyl anilino-5,8-dihydroxy anthraquinone, which has the ability to inhibit or minimize edge fog in light sensitive film products having a polyester substrate, the red azabenzanthrone or diazabenzanthrone dye is particularly useful in the form of an approximately &#39;&#39;&#39;&#39;neutral&#39;&#39;&#39;&#39; colored film substrate.

ilnited States Patent Hunter HEAT RESISTANT DYES FOR POLYESTER FILMPRODUCTS Inventor: C. Shelburn Hunter, 1669 Lake Ave., Rochester, NY.14650 Filed: Apr. 9, 1973 Appl. No.: 349,603

Related U.S. Application Data Division of Ser. No. 146,501, May 24,1971, Pat. No. 3,822,132, which is a continuation-in-part of Ser. No.822,032, May 5, 1969, abandoned,

U.S. Cl. 260/40 R, 96/84 R, 96/87 R Int. Cl C08g 51/14 Field of Search96/84 R, 87 R; 117/333,

References Cited UNITED STATES PATENTS 4/1973 Whyte 96/84 R 1 Dec. 10,1974 Primary Examiner--Ronald H. Smith Attorney, Agent, or Firm-E. W.Milan [57 ABSTRACT Certain azabenzanthrone and diazabenzanthrone dyeshave been found a. to be peculiarly resistant to spontaneous hightemperature degradation, and b. to be particularly useful as colorantsfor photographic film products made by extruding a dyed polyester filmbase.

18 Claims, No Drawings HEAT RESISTANT DYES FOR POLYESTER FILM PRODUCTSThis is a division, of application Ser. No. 146,501 filed May 24, i971,now U.S. Pat. No. 3,822,132, which patent application is acontinuation-in-part of U.S. Pat. application Ser. No. 822,032, filedMay 5, 1969, now abandoned.

The present invention relates to internally dyed polyester materials,particularly light sensitive film products having polyester substrates,which are resistant to the formation of edge fog.

It is well known that polyester polymers consisting mainly of linearchains of repeating residues of glycols containing from 2 to 12 carbonatoms and dicarboxylates containing from 4 to 20 carbon atoms haveunusually high melting points when their average molecular weights areabove about 20,000. For example, the melting point of commerciallyproduced poly(ethylene terephthalate) having an intrinsic viscosity of land a molecular weight of about 30,000 is about 264C, while the meltingpoints of many other linear polyesters of commercial importance todayare still higher. v

Because of their very high melting points, such polyester materialspresent an unusually difficult problem to dye chemists, whose task it isto compound a wide variety of colored polyesters for such importantmarkets as the textile and floor covering markets, and the like. Thatproblem relates to the generally relatively poor heat stability ofcolorant materials when polyesters containing the colorant materialsdispersed or dissolved therein are subjected to conventional commercialheat-forming operations. In such heat-forming operations, such asextruding films and fibers, for example, the mixture of polyester andcolorant must be maintained in the molten condition (at a temperatureabove the melting point of the polyester) for a fairly extended periodof time, of at least about 15 minutes usually, and sometimes as much as60 minutes or more. Under such extreme temperature conditions, almostevery organic dye material tested has been found to be insufficientlyheat stable to be acceptable for use as a colorant in heat-formedpolyester articles.

In order to qualify as an acceptable colorant for heat-formed polyesterarticles, a colorant must not only have the requisite heat stability,per se, but it must also have excellent color stability in the moltenpolyester environment at temperatures of at least about 275C for atleast 30 minutes (preferably for at least about 60 minutes to simulateactual production conditions). In addition, the colorant must becompatible with the polyester in amounts up to at least about 0.01weight percent, which includes most practical use levels. However,sometimes as little as 3 ppm has proven useful. Compatibility canreadily be ascertained by observing a blend of colorant with polyesterthat has been heated above 275C (and above the melting point of thepolyester) for l5-30 minutes. Incompatibility is evidenced by thegathering together in the polyester of distinct spots or fairly largeparticles of colorant.

Still another requirement that a truly widely useful colorant forpolyester articles must meet is that relating to the resistance of thecolorant, in the polyester environment, (wherein the polyester is inboth the molten and solidified states) to sublimation. Some organiccolorants that might otherwise be considered acceptable for use ascolorants in heat-formed polyester articles fail in this respect.Sublimation contributes to many undesirable effects, includinginstability of the color in the final product, and difficulty incontrolling (and reproducing) colors from the standpoint of themanufacturers of the heat-formed products. In addition, colorants foruse in photographic films must not poison the radiation sensitivelayers.

Hence, acceptable colorants for heat-molded polyester products must beat least (a) chemically (color) stable in the molten polyesterenvironment for an extended period of time, (b) compatible with thepolyesters at practical usage levels of at least about 0.01 weightpercent, and (c) must not sublime out of, or away from, the polyester,either in the molten state or in the solid state, even after a prolongedperiod of time.

It has now been discovered that certain azabenzanthrone anddiazabenzanthrone materials, surprisingly, have the requisite heatstability, compatibility and nonsublimation properties in the moltenpolyester environment to qualify them as acceptable colorants for thecommercial manufacture of colored, heat-formed polyester articles. Thematerials that have been discovered to have the requisite very highlevel of heat stability and l I W.

wherein R R R and R are selected from the group consisting of H, OI-I,--NI-Ihd 2, NO

substituted amino, amido, sulfonamido, alkyl, aryl, aralkyl, alkaryl',at least one R R R and R being other than H, and at most two of R,, R Rand R, having radical weights above about and R is the same as R1, R2R8, and R4 It is particularly advantageous that a wide range of colorsis represented by this group of materials, so that, by blending them,and by using one or more of them in combination with other compatiblecolorant materials,

a very wide range of tinted or colored materials can be H made using thecolorants of the present invention.

A particularly preferred group of the azabenzanthrone anddiazabenzanthrone colorant blends (with one or more of the polyestersdescribed hereinbefore) 5 include heat-formed compositions which containthe polyester(s) plus one or more of the following colorant materials.(The names in parenthesis after the name of the colorant is the tint ofthe colored polyester containing the colorant):

2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-ptoluenesulfonamido-3-azabenzanthrone(yellow) 2,3-dihydro-3-methyl-2-oxo-l-p-toluidino-3- azabenzanthrone(yellow) 6-amino-4-p'toluidino-l ,3-diazabenzanthrone (orange) l l N1122,3-dihydro-6-[N-3-(dimethylamino )-propylamino]-3- methyl-2-03ml-phenyl-3-azabenzanthrone (red) 4-p-chloroanilino-l ,3-diazabenzanthrone(orange) 2,3-dihydro-3-methyl-6-[ p-( l-methylbutyl )anilino}-2- oxol-phenyl-3-azabenzanthrone (violet) 4-anilino-6-[N-( 2,4-dichlorobenzoyl)amino -1 ,3-

3 diazabenzanthrone (orange) (g) V V H 2,3-dihydro-6-(2,4-dimethylanilino)-1-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone (violet)2,3-dihydro-6-p-chloroanilino-1-cya.no3-methyl-2- oxo-3-azabenzanthrone(blue) a 2,3-dihydro-3-methyl-2oxo-6-p-toluidino-3- azabenzanthrone(red) 5 V ..W.Wt 4 A ,V- W

2,3-dihydro-6-(4 -t-amylanilino)- l -ethoxycarbonyl-3-methyl-2-oxo-3-azabenzathrone (magenta) phenyl-3-azabenzathrone(magenta) It is noteworthy that, whereas the azabenzanthrone anddiazabenzanthrone materials described above can be genericallyconsidered to be anthracene-derived 5 5 dyes, it is recognized that byfar the greater majority of 2,3-dihydrol-ethoxycarbonyl-3-methyl-2-oxo-6-ptoluidino-3-azabenzanthrone (magenta)r .t V

I *\f 1vcm2,3-dihydro-l-ethoxycarbonyl-3-methyl-2-oxo-6-mtoluidino-3-azabenzanthrone(magenta) 2,3-dihydro- 1-ethoxycarbonyl-3-methyl-2-oxo-6-otoluidino-3-azabenzanthrone (magenta)such anthracene-type dyes (including many anthraquinone-type dyes) areeither unstable or incompatible in polyester systems such as those aboutwhich the present invention is concerned. For example, dyes of thefollowing type have been found to spontaneously degrade excessively whenthey are held in molten poly- (ethylene terephthalate) for one hour at atemperature of fi the r QQPPm QM H x x O Mx x M w. 0 5 6 6 H3. m C C Nl,4,5,8-tetraanilino anthraquinone l, -bis-cyclohexyl anthraquinoneO-GH:

1 ,4-bis-p-methoxyanilino-5 ,S-dihydroxy anthraquinone 1,4-diaminoanthraquinone 1-amino-4-acetamido anthraquinone l-amino-4-anilin0anthraquinone l ,4-dihydr0xy-5 ,8-di-B-hydroxyethylamino anthraquinone1,4-diamylamino anthraquinone X cycluhexy! 1,4-diamino-8-nitroanthraquinone in one of the preferred embodiments of the presentinvention, a red azabenzanthrone is used in combination with aheat-stable, compatible, non-subliming green dye in a thin polyesterfilm (0.5 to 30 mils in thickness) in order to yield a substrate for aphotographic film which is essentially neutral in color and in which theproblem of edge fog is minimized. Examples of this preferred embodimentis the use of a combination of a red azabenzanthrone dye such as2,3-dihydro-3-methyl 2-oxo-6-p-toluidino-3-azabenzanthrone (I) witheither (or a mixture thereof) 1,4-dihydrxy-5,8-di-p-toluidino-anthraquinone (II) or 1,4-di-p-butylanilino-5,8-dihydroxy anthraquinone (III), which are stable, compatiblegreen dyes. Dyes II and III are particularly valuable for use inpolyester film bases not only because of their excellent hightemperature stability and compatibility but also because they rank amongthe very few dyes (necessary in this end use in combination with astable, compatible red dye to obtain a neutral color in the film base)that absorb efficiently in the near infra-red (700-800 nm) region of theelectromagnetic spectrum. It is apparently this peculiar. ability ofabsorb efficiently in the near infra-red region of the spectrum thatcauses these dye combinations to inhibit edge fog so markedly when theyare used in suf-' ficiently small amounts in the film base to createacceptable, low optical densities. For example, in a typical commercialphotographic film product having a 4mil thick poly(ethyleneterephthalate) substrate, whereas only about 0.1 optical density isgenerally adequate to prevent most edge fog, it is often desirable forother reasons well known to the photographic art that the opticaldensity of the substrate be at most about 0.5, and preferably at mostabout 0.35 (for panchro-' matic films) and at most about 0.15 for colorfilms. See the disclosure of US. Pat. No. 2,622,026 for details aboutred cyan dye combinations useful in cellulose ester film substrates.

A detailed example of a particularly preferred em bodiment of thepresent invention is the use of 88 parts per million of2,3-dihydro-3-methyl-2-oxo-6-ptoluidino-3-azabenzanthrone (a red dye)and 144 parts per million ofl,4-dihydroxy-5,8-di-p-toluidinoanthraquinone (a green dye) in apolyester film base which has a layer of conventional photographicemulsion over one surface. Another particularly preferred embodiment ofthis aspect of the present invention .is the use of 80 parts per millionof the same red azabenzanthrone dye with 140 parts per million of1,4-di-pbutyl anilino-5,8-dihydroxy anthraquinone (green) in anotherwise conventional photographic film element having a polyester(containing these dyes) substrate. in these particularly preferredembodiments, the visually neutral color can be obtained by simplybalancing appropriate amounts of the respective red and green dyes. Ingeneral, however, the amount of red dye can be varied from about 40 toabout 600 parts per million, while the green dye can be varied fromabout 60 to about 1,000 parts per million. Greater amounts can be used,but the optical density of the film base (or the resulting negativeafter exposure and development of the sensitized article) shouldpreferably be at most about 0.3 unless it is preferred that theresulting developed article not be used as a transparency.

Other materials, such as plasticizers, other colorant materials, anddispersions (such as carbon, titanium dioxide, and/or silica) can alsobe present in the colored, heat-formed compositions of this invention.Particularly preferred polyesters for use in the practice of thisinvention include poly(ethylene terephthalate) andpoly(l,4-cyclohexylenedimethylene terephthalate) and copolymerscontaining them.

The polyester compositions of this invention can be manufactured by anyof a number of methods which will be manufactured by any of a number ofmethods which will be immediately evident to those artisans in thisfield. Thus, the powdered colorant can simply be mechanically blendedwith granules, pellets or flakes of the polyester in appropriate amountsat any time prior to the point where the polyester is melted andheatformed. Or, if desired, a concentrate or dye and polyester can beprepared separately, and then blended with more of the polyester asdesired or needed to accomplish the final colored, heat-formed article.Colorants can also be present when the polyester is formed. Heat-formingcan be accomplished in any manner desired, in which manner the blend ofcolorant and polyester is melted (or sufficiently softened to cause itto take a particular form), heat-formed by extrusion or compression orvacuum molding, for example, and then cooled and solidified. Forexample, the heatformed articles of this invention include (but are notlimited to) films, coatings, molded articles, fibers, and the like. Thearticles can also be processed in any of a number of ways subsequent tothe heataforming, without detracting from any of the benefits that canbe obtained by practicing this invention. For example, they can be cut,spliced, punched, subjected to crystalliza- -tion, even chopped intosmall pieces, and even remelted and heat-formed again, if .desired.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:

l. A colored polyester film article having a thickness of from about 0.5to about 30 mils, an optical density of at most about 0.5, and auniform, approximately neutral color; said film article containing ablend of dyes, which blend consists essentially of the red dye 2,-3-dihydro-3-methyl-2-oxo-6-p-toluidino 3- azabenzanthrone and the greendye l,4-dihydroxy-5,8- di-p-toluidino anthraquinone.

2. A article as in claim 1, wherein said polyester consists essentiallyof poly(ethylene terephthalate).

'3. An article as in claim 1, wherein said polyester consistsessentially of poly( l ,4-dimethylenecyclohexylene terephthalate).

4. A colored polyester article, comprising a blend of (l) at least oneazabenzanthrone or diazabenzanthrone dye selected from the group of dyeshaving structures:

wherein R R R and R are selected from the group consisting of -H, -OH,-NH -NO;,

N-3(dimethylamino)-propylamin0, N-(2,4- dichlorobenzoyl) amino, 4't-amylanilino, pchloranilino, 2,4-dimethylanilino, p-( 1-methybutyl)aniiino, o, m-, and p-toluidino, amido, sulfonamido, alkyl,aryl, and alkaryl; at least one of R R R and R being other than H, andat most two of R R R and R having radical weights above about 70; and Ris the same as R R R or R and (2) at least one green dye selected fromthe group consisting of l,- 4-dihydroxy-5,S-di-p-toluidino anthraquinoneand 1,4- di-p-butyl anilino-5,8-dihydroxy anthraquinone, said green dyebeing l,4-dihydroxy-5,S-di-p-toluidino anthraquinone when saidazabenzanthrone or diazabenzanthrone dye is selected from group (A) or(B) and when said green dye is 1,4-di-p-butyl aniiino-5,8- dihydroxyanthraquinone, said azabenzanthrone or diazabenzanthrone dye is selectedfrom group (B).

5. An article as in claim 4, wherein said green dye is1,4-dihydroxy-5,8-di-p-toluidino anthraquinone and saiddiazabenzanthrone dye is NAN A R3 VUV lli'a wherein R and R are selectedfrom the group consist ing of -H, -OH, z

6. An article as in claim 5, wherein said diazabenzanthrone dye is6-amino-4-p-toluidinol ,3- diazabenzanthrone, 4-p-chloroanilinol ,3-diazabe nzanthrone, or 4-an ilino 6- N-( 2,4-

dichlorobenzoyl )aminol-l ,3-diazabenzanthronei 7. An article as inclaim 4, wherein said green dye is l,4-dihydroxy-5,8-di-p-toluidinoanthraquinone and said azabenzanthrone dye is wherein R R R and R areselected from the group consisting of -H, -OH, -NH

N-3 dimethylamino )-propylamino, N-( 2,4- dichlorobenzoyl) amino,4'-t-amylanilino, pchloranilino, 2 ,4-dimethylanilino, p-(lmethylbutyl)anilino, 0-, m-, and p-toluidino amido, sulfonamido, alkyl,aryl, and alkaryl; at least one of R R R and R being other than H, andat most two of R R R and R having radical weights above about and R isthe same as R R R or R 8. An article as in claim 7, wherein said greendye is 1,4-dihydroxy-5,8-di-p-toluidino anthraquinone and saidazabenzanthrone dye is 2,3-dihydro-lethoxycarbonyl-S-methyl-2-oxo-6ptoluenesulfonamido-3-azabenzanthrone, 2,3-dihydr0- 3-methyl-2-oxol-p-toluidino- 3-azabencanthrone, 2, 3-dihydro-6-[N-B-(dimethylamino)-propylamino]-3- methyl-Z-oxo- 1phenyl-3-azabenzanthrone, dihydro-3-methyl-6- [p-(l-methyl-butyl)anilino1-2- oxol-phenyl-3-azabenzanthrone,2,3-dihydro-6-( 2,4- dimethyl-anilino l -ethoxycarbonyl-3-methyl-2-oxo-3- azabenzanthrone, 2,3-dihydro-6-p-chlor0anilino-1cyano-3-methyl-2-oxo-3-azabenzanthrone, 2,3- dihydrol-ethoxycarbonyl-3-methyl-2-oxo-6-ptoluidino-3-azabenzanthrone, 2,3-dihydrolethoxycarbonyl-S-methyl-2-oxo-6-m-toluidino-3-azabenzanthrone, 2,3-dihydrol -ethoxycarbonyl-3-methyl-2-oxo-6-o-toluidino-3-azabenzanthrone, 2,3-dihydro-3-methyl-2-oxo6-p-toluidino-3- azabenzanthrone,2,3-dihydro-6-(4't-amylanilino)- lethoxycarbonyl-3-rnethyl-2-oxo-3-azabenzanthrone, or 2 ,3-dihydro-3-methyl-6-( 2,4-dimethylanilino l phenyl-Ei-azabenzanthrone.

9. An articie as in claim 4, wherein said green dye is 1,4-di-butylaniline-5.8-dihydroxy anthraquinone and said diazabenzanthrone dye iswherein R and R are selected from the group consisting of -H, -OH, -NHp-NO N-3(dimethylamino)-propylamino, N-(2,4- dichlorobenzoyl) amino,4'-t-amylanilino, pchloroanilino, 2,4-dimethylanilino, p-(lmethylbutyl)anilino, o-, m-, and p-toluidino, amido, sulfonamido,alkyl, aryl, and alkaryl; at least one of R and R being other than H,and at most two of R R R and R having radical weights above about 70;and R is the same as R or R 10. An article as in claim 9 wherein saiddiazabenzanthrone dye is 6-amino-4-p-toluidino-l ,3- diazabenzanthrone,4-p-chloroanilino-l ,3- diazabenzanthrone or 4-anilino-6-[N-(2,4-

dichlorobenzoyl) amino]-1 ,3-diazabenzanthrone.

11. An article as in claim 4, wherein said polyester is a linearpolyester of repeating polymethylene glycol and diacyl radicals, thenumber of carbon atoms in the polymethylene groups being from 2 to 8.

12. An article as in claim 4, wherein said polyester is poly(ethyleneterephthalate).

13. An article as in claim 4, wherein said polyester is poly( l,4-dimethylenecyclohexylene terephthalate).

14. A fiber article according to claim 4.

15. A molded article according to claim 4.

16. A colored polyester article having an approximately neutral color;said article comprising the red dye2,3-dihydro-3-methyl-2-oxo-6-p-toluidino-3- azabenzanthrone and thegreen dye l,4-dihydroxy-5,8- di-p-toluidino anthraquinone.

17. An article according to claim 16 containing from about 40 to about600 parts of said red dye and from about 60 to about 1,000 parts of saidgreen dye per million parts of said colored polyester.

18. A film article comprising a colored polyester film substrate; saidsubstrate comprising at least two different types of dyes selected from(a) the following group A azabenzanthrone dyes or group Bdiazabenzanthrone dyes:

A. 2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-toluenesulfonamido-3-azabenzanthrone, 2,3-dihydro-3-methyl-2-oxo-l-p-toluidino-3- azabenzanthrone,2,3-dihydro-6-[N-3- (dimethylamino )-propylamino] -3-methyl-2-oxo- 1-phenyl-3-azabenzanthrone, 2,3-dihydro-3-methyl- 6-[p-(1-methylbutyl)anilino]-2-oxol -phenyl-3- azabenzanthrone,2,3-dihydro-6-(2,4-dimethylanilino)-l -ethoxycarbonyl-3 -methyl-2-oxo-3-azabenzanthrone, 2,3-dihydro-6-p-chloroanilino- 1cyano-3-methyl-2-oxo-3-azabenzanthrone, 2,3- dihydrol -ethoxycarbonyl-3-methyl-2-oxo-6-ptoluidino-3-azabenzanthrone, 2,3-dihydro-1-ethoxycarb0nyl-3-methyl-2-oxo-6-m-toluidino-3- azabenzanthrone,2,3-dihydro-l-ethoxycarbonyl-3-methyl-2-oxo-6-o-toluidino-3-azabenzanthrone,2,3-dihydro-3-methyl-2-oxo-6-p-toluidino-3- azabesnzanthrone,2,3-dihydro-6-(4'-tamylanilino)-l-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone or 2,3-dihydro-3-methyl-6-(2,4- dimethylanilino l-phenyl-3-azabenzanthrone, or

B 6-amino-4-p-toluidino-l,3-diazabenzanthrone, 4-p-chloroanilino-l,3-diazabenzanthrone, or 4-anilino-6-[N-(2,4-dichlorobenzoyl)amino1-1,3- diazabenzanthrone, and

at least one green dye selected from the group consisting ofl,4-dihydroxy-5,8-di-p-toluidino anthraquinone and 1,4-di-p-butylanilino-5,8-dihydroxy anthraquinone, said green dye beingl,4-dihydroxy-5,8-di-ptoluidino anthraquinone when said azabenzanthroneor diazabenzanthrone dye is selected from group (A) or (B), when saidgreen dye is 1,4-di-p-butyl aniline-5,8- dihydroxy anthraquinone, saidazabenzanthrone or diazabenzanthrone dye is selected from group (B).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 0 Patent No.3J853:8O7 Dated December 97 Inventor(s) C. Shleburn Hunter It iscertified that error appears in the above-identified patent Q and thatsaid Letters Patent are hereby corrected as shown below:

Amend the title to read Heat Resistant Dyes for Polyester Products Amendheading to include the assignee, Eastman Kodak: Company, Rochester,

Column 2, line 5%, NHhd2" should be NH Q Column 10, lines 9 and 10,delete manufactured by any of a number of methods which will be Column10, line 15, change "or to of I Column 12, line 37, changeazabencanthrone to Q azabenzanthrone Signed and Scaled this twenty-sixthDay Of August 1975 Q [SEAL] Arrest:

RUTH c. MASON c. MARSHALL DANN e AIIPSII'NR ()ffi't (ummissiuneraj'Parents and Trademarks

1. A COLORED POLYESTER FILM ARTICLE HAVING A THICKNESS OF FROM ABOUT 0.5TO ABOUT 30 MILS, AN OPTICAL DENSITY OF AT MOST ABOUT 0.5, AND AUNIFORM, APPROXIMATELY NEUTRAL COLOR; SAID FILM ARTICLE CONTAINING ABLEND OF DYES, WHICH BLEND CONSISTS ESSENTIALLY OF THE RED DYE2,3-DIHYDRO-3-METHYL-2-OXO-6-PTOLUIDINO-3-AZABENZANTHRONE AND THE GREENDYE 1,4DIHYDROXY-5,8-DI-P-TOLUIDINO ANTHRAQUINONE.
 2. A article as inclaim 1, wherein said polyester consists essentially of poly(ethyleneterephthalate).
 3. An article as in claim 1, wherein said polyesterconsists essentially of poly(1,4-di-methylenecyclohexyleneterephthalate).
 4. A colored polyester article, comprising a blend of(1) at least one azabenzanthrone or diazabenzanthrone dye selected fromthe group of dyes having structures:
 5. An article as in claim 4,wherein said green dye is 1,4-dihydroxy-5,8-di-p-toluidino anthraquinoneand said diazabenzanthrone dye is
 6. An article as in claim 5, whereinsaid diazabenzanthrone dye is6-amino-4-p-toluidino-1,3-diazabenzanthrone,4-p-chloroanilino-1,3-diazabenzanthrone, or 4-anilino6-(N-(2,4-dichlorobenzoyl)amino)-1,3-diazabenzanthrone.
 7. An article asin claim 4, wherein said green dye is 1,4-dihydroxy-5,8-di-p-toluidinoanthraquinone and said azabenzanthrone dye is
 8. An article as in claim7, wherein said green dye is 1,4-dihydroxy-5,8-di-p-toluidinoanthraquinone and said azabenzanthrone dye is2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-p-toluenesulfonamido-3-azabenzanthrone,2,3-dihydro-3-methyl-2-oxo-1-p-toluidino-3-azabencanthrone,2,3-dihydro-6-(N-3-(dimethylamino)-propylamino)-3-methyl-2-oxo-1phenyl-3-azabenzanthrone,2,3-dihydro-3-methyl-6-(p-(1-methyl-butyl)anilino)-2-oxo-1-phenyl-3-azabenzanthrone,2,3-dihydro-6-(2,4-dimethyl-anilino)-1-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone,2,3-dihydro-6-p-chloroanilino-1-cyano-3-methyl-2-oxo-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-p-toluidino-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-m-toluidino-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-o-toluidino-3-azabenzanthrone,2,3-dihydro-3-methyl-2-oxo-6-p-toluidino-3-azabenzanthrone,2,3-dihydro-6-(4''t-amylanilino)-1-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone, or2,3-dihydro-3-methyl-6-(2,4-dimethylanilino)-1-phenyl-3-azabenzanthrone.9. An article as in claim 4, wherein said green dye is 1,4-di-butylanilino-5,8-dihydroxy anthraquinone and said diazabenzanthrone dye is10. An article as in claim 9 wherein said diazabenzanthrone dye is6-amino-4-p-toluidino-1,3-diazabenzanthrone,4-p-chloroanilino-1,3-diazabenzanthrone or4-anilino-6-(N-(2,4-dichlorobenzoyl) amino)-1,3-diazabenzanthrone. 11.An article as in claim 4, wherein said polyester is a linear polyesterof repeating polymethylene glycol and diacyl radicals, the number ofcarbon atoms in the polymethylene groups being from 2 to
 8. 12. Anarticle as in claim 4, wherein said polyester is poly(ethyleneterephthalate).
 13. An article as in claim 4, wherein said polyester ispoly(1, 4-dimethylenecyclohexylene terephthalate).
 14. A fiber articleaccording to claim
 4. 15. A molded article according to claim
 4. 16. Acolored polyester article having an approximately neutral color; saidarticle comprising the red dye2,3-dihydro-3-methyl-2-oxo-6-p-toluidino-3-azabenzanthrone and the greendye 1,4-dihydroxy-5,8-di-p-toluidino anthraquinone.
 17. An articleaccording to claim 16 containing from about 40 to about 600 parts ofsaid red dye and from about 60 to about 1,000 parts of said green dYeper million parts of said colored polyester.
 18. A film articlecomprising a colored polyester film substrate; said substrate comprisingat least two different types of dyes selected from (a) the followinggroup A azabenzanthrone dyes or group B diazabenzanthrone dyes: A.2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-toluenesulfonamido-3-azabenzanthrone,2,3-dihydro-3-methyl-2-oxo-1-p-toluidino-3-azabenzanthrone,2,3-dihydro-6-(N-3-(dimethylamino)-propylamino)-3-methyl-2-oxo-1-phenyl-3-azabenzanthrone,2,3-dihydro-3-methyl-6-(p-(1-methylbutyl)anilino)-2-oxo-1-phenyl-3-azabenzanthrone,2,3-dihydro-6-(2,4-dimethyl-anilino)-1-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone,2,3-dihydro-6-p-chloroanilino-1-cyano-3-methyl-2-oxo-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-p-toluidino-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-m-toluidino-3-azabenzanthrone,2,3-dihydro-1-ethoxycarbonyl-3-methyl-2-oxo-6-o-toluidino-3-azabenzanthrone,2,3-dihydro-3-methyl-2-oxo-6-p-toluidino-3-azabesnzanthrone,2,3-dihydro-6-(4''-t-amylanilino)-1-ethoxycarbonyl-3-methyl-2-oxo-3-azabenzanthrone or2,3-dihydro-3-methyl-6-(2,4-dimethylanilino)-1-phenyl-3-azabenzanthrone,or B 6-amino-4-p-toluidino-1,3-diazabenzanthrone,4-p-chloroanilino-1,3-diazabenzanthrone, or4-anilino-6-(N-(2,4-dichlorobenzoyl)amino)-1,3-diazabenzanthrone, and atleast one green dye selected from the group consisting of 1,4-dihydroxy-5,8-di-p-toluidino anthraquinone and 1,4-di-p-butylanilino-5,8-dihydroxy anthraquinone, said green dye being1,4-dihydroxy-5,8-di-p-toluidino anthraquinone when said azabenzanthroneor diazabenzanthrone dye is selected from group (A) or (B), when saidgreen dye is 1,4-di-p-butyl anilino-5,8-dihydroxy anthraquinone, saidazabenzanthrone or diazabenzanthrone dye is selected from group (B).